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The title compound is a bis-dimedone derivative which crystallizes as a monohydrate, C23H28O5·H2O. Its crystal packing is stabilized by hydrogen bonds involving water.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001593/na6040sup1.cif
Contains datablocks rd12, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001593/na6040Isup2.hkl
Contains datablock I

CCDC reference: 159757

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.041
  • wR factor = 0.115
  • Data-to-parameter ratio = 17.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

Comment top

Some years ago, we have accidentally encountered the twinned crystal structures of two similar compounds bearing the bis-dimedone moiety: bis(2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexenyl)phenylmethane (Bolte, Degen & Rühl, 1997) and 2,2'-methylenebis(3-hydroxy-5,5-dimethylcyclohex-2-en-1-one) (Bolte & Scholtyssik, 1997). Since these compounds can easily be prepared (Hünig et al., 1979) we have decided to synthesize various derivatives with the objective to find out if these are also twinned (Bolte et al., 2001). We hoped to find more twinned crystal structures in order to understand why some of these simple compounds containing the common bis-dimedone skeleton are twinned. Unfortunately, neither any of these nor the title compound, (I), turned out to be twinned.

The two cyclohexenone rings display envelope conformations with C14 and C24 deviating by 0.644 (2) and 0.653 (2) Å, respectively, from the plane of the remaining five ring atoms. Both apices are extended towards the phenyl ring. Two strong intramolecular hydrogen bonds are formed connecting the two cyclohexenone rings. The water molecule bridges two different molecules via its H atoms and acts as an acceptor for the H atom of the hydroxyl group of a third molecule.

Experimental top

The title compound was synthesized according to Nagarajan & Shenoy (1992).

Refinement top

All H atoms were located by difference Fourier synthesis and refined with fixed individual displacement parameters [U(H) = 1.5Ueq(Cmethyl) or U(H) = 1.2Ueq(C)] using a riding model with C—H(aromatic) = 0.95, CH(methyl) = 0.98, C—H(secondary) = 0.99 or C—H(tertiary) = 1.00. A l l hydroxyl H atoms were refined isotropically.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.
(rd12) top
Crystal data top
C23H28O5·H2OF(000) = 864
Mr = 402.47Dx = 1.221 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.948 (1) ÅCell parameters from 8192 reflections
b = 27.128 (3) Åθ = 0–25°
c = 9.045 (1) ŵ = 0.09 mm1
β = 94.30 (1)°T = 173 K
V = 2189.4 (4) Å3Block, colourless
Z = 40.70 × 0.65 × 0.45 mm
Data collection top
Siemens CCD three-circle
diffractometer
4836 independent reflections
Radiation source: fine-focus sealed tube4088 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scansθmax = 27.1°, θmin = 2.4°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1111
Tmin = 0.941, Tmax = 0.962k = 3434
41555 measured reflectionsl = 1111
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115 w = 1/[σ2(Fo2) + (0.0615P)2 + 0.8381P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
4836 reflectionsΔρmax = 0.31 e Å3
283 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0036 (10)
Crystal data top
C23H28O5·H2OV = 2189.4 (4) Å3
Mr = 402.47Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.948 (1) ŵ = 0.09 mm1
b = 27.128 (3) ÅT = 173 K
c = 9.045 (1) Å0.70 × 0.65 × 0.45 mm
β = 94.30 (1)°
Data collection top
Siemens CCD three-circle
diffractometer
4836 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
4088 reflections with I > 2σ(I)
Tmin = 0.941, Tmax = 0.962Rint = 0.028
41555 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.31 e Å3
4836 reflectionsΔρmin = 0.17 e Å3
283 parameters
Special details top

Experimental. ;

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.29361 (13)0.13075 (4)0.54834 (13)0.0198 (2)
H10.40340.13580.54060.024*
C110.28443 (13)0.08187 (4)0.63200 (13)0.0194 (2)
C120.15444 (14)0.05409 (4)0.63776 (13)0.0204 (2)
O120.02302 (10)0.06934 (3)0.57925 (10)0.0250 (2)
H120.017 (3)0.1092 (10)0.565 (3)0.094 (8)*
C130.14973 (14)0.00474 (4)0.71296 (14)0.0230 (3)
H13A0.08110.01710.65220.028*
H13B0.10740.00910.81010.028*
C140.30308 (15)0.02096 (5)0.73807 (14)0.0240 (3)
C170.35423 (16)0.04164 (5)0.59148 (15)0.0295 (3)
H17A0.36250.01460.52050.044*
H17B0.28080.06580.55060.044*
H17C0.45200.05770.61000.044*
C180.28982 (18)0.06367 (5)0.84774 (16)0.0346 (3)
H18A0.38700.08030.86410.052*
H18B0.21460.08720.80700.052*
H18C0.25940.05080.94210.052*
C150.41524 (15)0.01758 (5)0.80366 (14)0.0253 (3)
H15A0.39250.02450.90710.030*
H15B0.51720.00330.80680.030*
C160.41507 (14)0.06573 (4)0.71962 (13)0.0217 (3)
O160.53345 (10)0.09202 (3)0.73513 (11)0.0284 (2)
C210.24629 (14)0.17507 (4)0.63908 (13)0.0224 (3)
C220.35272 (15)0.20166 (5)0.72617 (14)0.0243 (3)
O220.49556 (11)0.18933 (4)0.74452 (11)0.0328 (2)
H220.513 (3)0.1514 (11)0.730 (3)0.105 (9)*
C230.31470 (16)0.24720 (5)0.81107 (15)0.0298 (3)
H23A0.39970.27050.81110.036*
H23B0.30250.23790.91530.036*
C240.17178 (16)0.27352 (5)0.74844 (15)0.0300 (3)
C270.1986 (2)0.29882 (5)0.60019 (17)0.0417 (4)
H27A0.10660.31550.56160.063*
H27B0.22700.27400.52870.063*
H27C0.27940.32310.61600.063*
C280.1266 (2)0.31269 (6)0.86021 (18)0.0410 (4)
H28A0.03560.32960.82030.061*
H28B0.20790.33670.87730.061*
H28C0.10760.29670.95410.061*
C250.04799 (16)0.23432 (5)0.72627 (16)0.0311 (3)
H25A0.01730.22430.82480.037*
H25B0.04020.24940.67130.037*
C260.09214 (14)0.18863 (5)0.64370 (14)0.0241 (3)
O260.01393 (11)0.16289 (4)0.58288 (11)0.0313 (2)
C310.22749 (13)0.13039 (5)0.38573 (13)0.0218 (3)
C320.21582 (14)0.08646 (5)0.30472 (13)0.0238 (3)
H320.23840.05600.35320.029*
C330.17118 (16)0.08683 (5)0.15254 (14)0.0290 (3)
O330.15874 (14)0.04450 (4)0.07038 (11)0.0417 (3)
H330.174 (3)0.0167 (9)0.128 (3)0.067 (7)*
C340.13794 (18)0.13137 (6)0.08035 (15)0.0367 (3)
H340.10750.13180.02250.044*
C350.14979 (19)0.17503 (6)0.16041 (16)0.0364 (3)
H350.12700.20540.11160.044*
C360.19483 (16)0.17490 (5)0.31197 (15)0.0294 (3)
H360.20330.20510.36500.035*
O1W0.80268 (13)0.03988 (4)0.77648 (13)0.0409 (3)
H1W0.720 (3)0.0598 (8)0.765 (2)0.065 (6)*
H2W0.873 (3)0.0512 (9)0.708 (3)0.077 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0205 (6)0.0188 (6)0.0202 (6)0.0001 (4)0.0012 (4)0.0001 (4)
C110.0224 (6)0.0188 (5)0.0171 (5)0.0014 (4)0.0021 (4)0.0008 (4)
C120.0228 (6)0.0223 (6)0.0162 (5)0.0023 (5)0.0015 (4)0.0027 (4)
O120.0207 (4)0.0252 (5)0.0289 (5)0.0006 (3)0.0005 (3)0.0012 (4)
C130.0256 (6)0.0205 (6)0.0229 (6)0.0018 (5)0.0031 (5)0.0002 (5)
C140.0304 (7)0.0203 (6)0.0211 (6)0.0022 (5)0.0015 (5)0.0015 (5)
C170.0360 (7)0.0253 (6)0.0277 (7)0.0051 (5)0.0055 (5)0.0017 (5)
C180.0477 (9)0.0255 (7)0.0306 (7)0.0024 (6)0.0028 (6)0.0074 (6)
C150.0276 (6)0.0247 (6)0.0231 (6)0.0033 (5)0.0024 (5)0.0027 (5)
C160.0235 (6)0.0221 (6)0.0195 (6)0.0019 (5)0.0018 (5)0.0031 (5)
O160.0214 (4)0.0266 (5)0.0366 (5)0.0005 (4)0.0029 (4)0.0009 (4)
C210.0275 (6)0.0189 (6)0.0207 (6)0.0006 (5)0.0009 (5)0.0008 (4)
C220.0278 (6)0.0222 (6)0.0229 (6)0.0001 (5)0.0011 (5)0.0001 (5)
O220.0284 (5)0.0301 (5)0.0391 (6)0.0015 (4)0.0026 (4)0.0068 (4)
C230.0352 (7)0.0258 (7)0.0279 (7)0.0007 (5)0.0005 (5)0.0070 (5)
C240.0391 (8)0.0219 (6)0.0288 (7)0.0048 (5)0.0019 (6)0.0053 (5)
C270.0664 (11)0.0237 (7)0.0349 (8)0.0039 (7)0.0031 (7)0.0001 (6)
C280.0512 (9)0.0308 (8)0.0411 (8)0.0070 (7)0.0043 (7)0.0127 (6)
C250.0306 (7)0.0296 (7)0.0333 (7)0.0069 (5)0.0030 (6)0.0052 (6)
C260.0270 (6)0.0231 (6)0.0221 (6)0.0016 (5)0.0011 (5)0.0014 (5)
O260.0277 (5)0.0279 (5)0.0376 (5)0.0002 (4)0.0017 (4)0.0025 (4)
C310.0216 (6)0.0247 (6)0.0191 (6)0.0007 (5)0.0025 (4)0.0014 (5)
C320.0268 (6)0.0242 (6)0.0207 (6)0.0023 (5)0.0027 (5)0.0014 (5)
C330.0348 (7)0.0320 (7)0.0203 (6)0.0016 (6)0.0038 (5)0.0030 (5)
O330.0672 (8)0.0355 (6)0.0221 (5)0.0031 (5)0.0011 (5)0.0060 (4)
C340.0499 (9)0.0420 (8)0.0179 (6)0.0061 (7)0.0006 (6)0.0035 (6)
C350.0522 (9)0.0315 (7)0.0255 (7)0.0070 (6)0.0027 (6)0.0086 (6)
C360.0400 (8)0.0240 (6)0.0242 (6)0.0027 (5)0.0027 (6)0.0018 (5)
O1W0.0325 (6)0.0479 (7)0.0433 (6)0.0122 (5)0.0094 (5)0.0140 (5)
Geometric parameters (Å, º) top
C1—C111.5319 (16)C23—C241.5354 (19)
C1—C211.5330 (16)C23—H23A0.9900
C1—C311.5437 (17)C23—H23B0.9900
C1—H11.0000C24—C251.538 (2)
C11—C121.3903 (17)C24—C281.5413 (19)
C11—C161.4309 (17)C24—C271.541 (2)
C12—O121.3193 (15)C27—H27A0.9800
C12—C131.5037 (17)C27—H27B0.9800
O12—H121.09 (3)C27—H27C0.9800
C13—C141.5407 (17)C28—H28A0.9800
C13—H13A0.9900C28—H28B0.9800
C13—H13B0.9900C28—H28C0.9800
C14—C181.5357 (18)C25—C261.5147 (18)
C14—C151.5372 (18)C25—H25A0.9900
C14—C171.5405 (18)C25—H25B0.9900
C17—H17A0.9800C26—O261.2699 (16)
C17—H17B0.9800C31—C321.3989 (17)
C17—H17C0.9800C31—C361.3996 (18)
C18—H18A0.9800C32—C331.4042 (18)
C18—H18B0.9800C32—H320.9500
C18—H18C0.9800C33—O331.3678 (17)
C15—C161.5112 (17)C33—C341.395 (2)
C15—H15A0.9900O33—H330.92 (2)
C15—H15B0.9900C34—C351.388 (2)
C16—O161.2759 (15)C34—H340.9500
C21—C221.3912 (18)C35—C361.3996 (19)
C21—C261.4312 (18)C35—H350.9500
C22—O221.3195 (16)C36—H360.9500
C22—C231.5069 (18)O1W—H1W0.92 (2)
O22—H221.05 (3)O1W—H2W0.97 (3)
C11—C1—C21112.78 (10)C22—C23—C24114.01 (11)
C11—C1—C31115.74 (10)C22—C23—H23A108.8
C21—C1—C31114.43 (10)C24—C23—H23A108.8
C11—C1—H1104.0C22—C23—H23B108.8
C21—C1—H1104.0C24—C23—H23B108.8
C31—C1—H1104.0H23A—C23—H23B107.6
C12—C11—C16117.67 (11)C23—C24—C25107.36 (11)
C12—C11—C1124.31 (11)C23—C24—C28109.31 (12)
C16—C11—C1117.82 (10)C25—C24—C28109.91 (12)
O12—C12—C11122.56 (11)C23—C24—C27110.38 (12)
O12—C12—C13113.97 (10)C25—C24—C27110.62 (12)
C11—C12—C13123.47 (11)C28—C24—C27109.24 (12)
C12—O12—H12113.4 (14)C24—C27—H27A109.5
C12—C13—C14114.50 (10)C24—C27—H27B109.5
C12—C13—H13A108.6H27A—C27—H27B109.5
C14—C13—H13A108.6C24—C27—H27C109.5
C12—C13—H13B108.6H27A—C27—H27C109.5
C14—C13—H13B108.6H27B—C27—H27C109.5
H13A—C13—H13B107.6C24—C28—H28A109.5
C18—C14—C15110.11 (11)C24—C28—H28B109.5
C18—C14—C17108.88 (11)H28A—C28—H28B109.5
C15—C14—C17110.63 (11)C24—C28—H28C109.5
C18—C14—C13109.00 (11)H28A—C28—H28C109.5
C15—C14—C13107.31 (10)H28B—C28—H28C109.5
C17—C14—C13110.90 (10)C26—C25—C24114.72 (11)
C14—C17—H17A109.5C26—C25—H25A108.6
C14—C17—H17B109.5C24—C25—H25A108.6
H17A—C17—H17B109.5C26—C25—H25B108.6
C14—C17—H17C109.5C24—C25—H25B108.6
H17A—C17—H17C109.5H25A—C25—H25B107.6
H17B—C17—H17C109.5O26—C26—C21122.45 (12)
C14—C18—H18A109.5O26—C26—C25116.71 (11)
C14—C18—H18B109.5C21—C26—C25120.82 (11)
H18A—C18—H18B109.5C32—C31—C36118.73 (11)
C14—C18—H18C109.5C32—C31—C1120.84 (11)
H18A—C18—H18C109.5C36—C31—C1120.00 (11)
H18B—C18—H18C109.5C31—C32—C33120.79 (12)
C16—C15—C14114.70 (10)C31—C32—H32119.6
C16—C15—H15A108.6C33—C32—H32119.6
C14—C15—H15A108.6O33—C33—C34117.85 (12)
C16—C15—H15B108.6O33—C33—C32122.15 (12)
C14—C15—H15B108.6C34—C33—C32120.00 (12)
H15A—C15—H15B107.6C33—O33—H33112.0 (14)
O16—C16—C11121.79 (11)C35—C34—C33119.32 (13)
O16—C16—C15117.28 (11)C35—C34—H34120.3
C11—C16—C15120.87 (11)C33—C34—H34120.3
C22—C21—C26118.06 (11)C34—C35—C36120.93 (13)
C22—C21—C1120.33 (11)C34—C35—H35119.5
C26—C21—C1121.52 (11)C36—C35—H35119.5
O22—C22—C21123.72 (12)C31—C36—C35120.23 (12)
O22—C22—C23113.41 (11)C31—C36—H36119.9
C21—C22—C23122.86 (12)C35—C36—H36119.9
C22—O22—H22112.4 (16)H1W—O1W—H2W107.4 (19)
C21—C1—C11—C1284.07 (14)C1—C21—C22—C23176.49 (11)
C31—C1—C11—C1250.38 (16)O22—C22—C23—C24157.55 (12)
C21—C1—C11—C1690.69 (13)C21—C22—C23—C2423.39 (18)
C31—C1—C11—C16134.86 (11)C22—C23—C24—C2549.45 (15)
C16—C11—C12—O12169.85 (11)C22—C23—C24—C28168.63 (12)
C1—C11—C12—O124.92 (18)C22—C23—C24—C2771.20 (15)
C16—C11—C12—C138.98 (17)C23—C24—C25—C2649.40 (15)
C1—C11—C12—C13176.26 (10)C28—C24—C25—C26168.19 (12)
O12—C12—C13—C14161.76 (10)C27—C24—C25—C2671.10 (15)
C11—C12—C13—C1419.32 (16)C22—C21—C26—O26171.09 (12)
C12—C13—C14—C18166.07 (11)C1—C21—C26—O265.44 (19)
C12—C13—C14—C1546.85 (13)C22—C21—C26—C257.23 (18)
C12—C13—C14—C1774.08 (13)C1—C21—C26—C25176.24 (11)
C18—C14—C15—C16168.56 (11)C24—C25—C26—O26158.78 (12)
C17—C14—C15—C1671.04 (14)C24—C25—C26—C2122.82 (18)
C13—C14—C15—C1650.06 (14)C11—C1—C31—C3224.09 (16)
C12—C11—C16—O16171.37 (11)C21—C1—C31—C32157.80 (11)
C1—C11—C16—O163.74 (17)C11—C1—C31—C36163.50 (11)
C12—C11—C16—C155.70 (17)C21—C1—C31—C3629.79 (16)
C1—C11—C16—C15179.19 (10)C36—C31—C32—C330.46 (19)
C14—C15—C16—O16157.08 (11)C1—C31—C32—C33172.97 (12)
C14—C15—C16—C1125.73 (16)C31—C32—C33—O33180.00 (12)
C11—C1—C21—C2292.42 (14)C31—C32—C33—C340.0 (2)
C31—C1—C21—C22132.51 (12)O33—C33—C34—C35179.85 (14)
C11—C1—C21—C2684.04 (14)C32—C33—C34—C350.1 (2)
C31—C1—C21—C2651.04 (15)C33—C34—C35—C360.2 (2)
C26—C21—C22—O22172.03 (12)C32—C31—C36—C350.7 (2)
C1—C21—C22—O224.55 (19)C1—C31—C36—C35173.30 (13)
C26—C21—C22—C236.94 (19)C34—C35—C36—C310.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O261.09 (3)1.49 (3)2.560 (1)164 (2)
O22—H22···O161.05 (3)1.62 (3)2.664 (1)171 (3)
O1W—H1W···O160.92 (2)1.88 (2)2.795 (2)172 (2)
O33—H33···O1Wi0.92 (2)1.76 (2)2.684 (2)174 (2)
O1W—H2W···O12ii0.97 (3)1.90 (3)2.870 (2)175 (2)
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC23H28O5·H2O
Mr402.47
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)8.948 (1), 27.128 (3), 9.045 (1)
β (°) 94.30 (1)
V3)2189.4 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.70 × 0.65 × 0.45
Data collection
DiffractometerSiemens CCD three-circle
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.941, 0.962
No. of measured, independent and
observed [I > 2σ(I)] reflections
41555, 4836, 4088
Rint0.028
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.115, 1.01
No. of reflections4836
No. of parameters283
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.31, 0.17

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O261.09 (3)1.49 (3)2.560 (1)164 (2)
O22—H22···O161.05 (3)1.62 (3)2.664 (1)171 (3)
O1W—H1W···O160.92 (2)1.88 (2)2.795 (2)172 (2)
O33—H33···O1Wi0.92 (2)1.76 (2)2.684 (2)174 (2)
O1W—H2W···O12ii0.97 (3)1.90 (3)2.870 (2)175 (2)
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z.
 

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